Polymerization catalyst

ABSTRACT

A novel olefin polymerization and copolymerization catalyst and method is provided wherein the catalyst is prepared by mixing an alkyl aluminum halide, a dialkyl magnesium compound and a reducible titanium compound of the formula Ti(OR) n  X 4-n  where R is an alkyl group, preferably of 1-6 carbon atoms, X is a halogen atom, and n is an integer between 0 and 4, inclusive, in the presence of a solvent and a particulate organic polymer whereby a reaction product is formed on the particles, and evaporating the solvent. The catalyst is active in the presence of an organometallic co-catalyst.

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of co-pending application Ser. No.912,874 filed June 5, 1978 and now abandoned.

BACKGROUND OF THE INVENTION

The catalyst of this invention is suitable for the polymerization andcopolymerization of ethylene and other 1-olefins, particularly of 2-8carbon atoms, and the copolymerization of these with 1-olefins of 2-20carbon atoms, such as propylene, butene and hexene, for example. It iswell suited for economical particle form and gas phase polymerizationprocesses. The active component of the catalyst is supported uponparticles of an organic polymer, the selection of which affects theparticle size, melt index and molecular weight distribution of theproduct polymer. Further, product bulk density is relatively high and iscontrollable by selection of the polymeric carrier.

SUMMARY OF THE INVENTION

An improved catalyst for the polymerization and copolymerization ofolefins is prepared by combining three reactive materials in thepresence of particles of an organic polymeric carrier. A reactionproduct of the three reactive materials is formed on and adheres to thecarrier and is activated by contact with an effective quantity of anorganometallic co-catalyst, such as trialkyl aluminum, for example.

The supported reaction product is believed to be a complex of the threereactive materials, and incorporates a major portion of the availabletitanium in a highly active form over a wide range of mole ratios of thereactants. Due to the inherent high reactivity of the complex, it is notnecessary to remove non-reactive titanium from the catalyst, but washingof the catalyst may be conducted, if desired.

The catalyst is, because of its high activity, well suited for use inthe particle form polymerization process in which the supportedcatalyst, the co-catalyst, and olefin monomer are contacted in asuitable solvent or in a gas phase process in which no solvent isnecessary.

The three reactive materials may be added to the carrier in any orderand comprise (1) an alkyl aluminum halide, (2) a dialkyl magnesiumcompound or a complex of dialkyl magnesium and alkyl aluminum compounds,and (3) a titanium alkoxide, a titanium alkoxide halide, or a titaniumhalide.

The alkyl aluminum halide is chosen from the group comprising dialkylaluminum halides, alkyl aluminum sesquihalides, and alkyl aluminumdihalides, with ethyl aluminum sesquichloride being preferred. Thetitanium compound is of the formula Ti(OR)_(n) X_(4-n) where R is analkyl group, X is a halogen atom, and n is an integer between 0 and 4,inclusive. A preferred titanium compound is titanium tetraisopropoxide.

Preferred dialkyl magnesium compounds are dibutyl magnesium, di-n-hexylmagnesium and butyl ethyl magnesium, any of which may be complexed withan alkyl aluminum compound, such as a trialkyl aluminum, to increase thesolubility of the magnesium compound and/or decrease the viscosity ofthe magnesium compound solution.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preparation of the Carrier

The reaction product catalyst of the invention forms and adheres to thesurface of polymeric carrier particles to a degree dependent upon thephysical and chemical nature of the carrier material. Similarly, thecharacteristics of the product polymer which grows from the catalystsurface is determined by the carrier characteristics.

In order for a particle form polymerization reaction to proceed bypolymer growth on the carrier, it is obviously necessary that thecarrier particles remain intact (i.e., not melt, dissolve or otherwisedegrade) under reaction conditions. Particle form polymerization may beconducted at temperatures up to 110° C. in a hydrocarbon solvent such asisobutane, for example. Therefore, a polymeric carrier which melts orotherwise degrades at temperatures up to 110° C., or which dissolves inisobutane or a similar solvent at these temperatures, is not a suitablecatalyst support.

Further, the carrier material must be substantially chemically inertwith respect to the catalyst formed thereon. It has been found that avery high concentration of polar groups in the carrier material resultsin reaction of the catayst forming reactants with the carrier andtherefore should be avoided. However, a relatively small amount of polargroups in the carrier is useful in promoting adherence and uniformdistribution of the catalyst thereon. Such adherence may also bepromoted by blending up to about 20 percent of an amorphous or onlyslightly crystalline hydrocarbon polymer into a predominantlycrystalline polymeric carrier material.

It has been found that production of carrier particles by grinding ofcarrier material results in a carrier surface which promotes adherenceof the catalyst to the carrier. The technique known as cryogenicgrinding is especially preferred. The carrier particles may range indiameter from about 20 microns to about 5 millimeters.

For use in automatic catalyst feeding valves commonly used in particleform polymerization plants, relatively small particles are generallypreferred, although alternate methods of feeding can be employed forlarger carrier particles. In addition, normal feeding valves operatemost effectively with materials having flow characteristics similar tothose of commonly used silica catalysts. Approximately spherical carrierparticles are especially suitable for use in such automatic valves.Furthermore, flow properties of the carrier are improved by the additionof a small amount, such as up to about 10% by weight, of pyrogenicsilica such as the silica having the trade name Cab-O-Sil, for example.

Specific examples of suitable carrier materials are high densitypolyethylene and isotactic polypropylene. U.S. Pat. No. 3,873,643,assigned to the assignee hereof, provides an excellent example of apolymer which contains low concentrations of polar groups and which issuitable for use as a carrier in this invention. The material of U.S.Pat. No. 3,873,643 comprises high density polyethylene grafted withorganic anhydrides.

More specifically, the polymers disclosed in Wu et at. U.S. Pat. No.3,873,643 are characterized as copolymers comprising polyolefins whichare modified by grafted cyclic and polycyclic unsaturated acid or acidanhydride monomers, or both, which exhibit improved compatability withother materials, and which are chemically reactive.

By polyolefins, it is meant polymers and copolymers of ethylene,propylene, butenes and other unsaturated aliphatic hydrocarbons.Suitable polyolefins include ethylene homopolymers prepared by lowpressure methods (linear or high density polyethylenes) and copolymersof ethylene with up to 40 weight percent of such higher olefins aspropylene, 1-butene and 1-hexene. The copolymers may contain up to 5% ofsuch di- or triolefins which are used commercially in ethylene-propyleneterpolymers such as ethylidene-norbornene, methylenenorbornene,1,4-hexadiene and vinylnorbornene. Also, it is preferable sometimes tograft to blends of two or more of the above homopolymers, copolymers andterpolymers.

By cyclic and polycyclic unsaturated acids and anhydrides, it is meantcompounds which contain one or more carboxylic and/or heterocyclicmoieties not including the anhydride ring. The rings may be simple,fused, bridged, spiro, joined directly, joined through aliphatic chainscontaining one or more carbon, oxygen or sulfur atoms, or combinationsof the above ring arrangements. These classes are representedrespectively by the following structures which are meant to beillustrative rather than limiting: ##STR1##

Rings may contain 3 to 8 atoms but generally 5 and 6 membered rings arepreferred. The monomer may contain aromatic rings but at least one ringshould be aliphatic. The olefinic bond is preferably unconjugated withthe acid or anhydride groups. Such conjugated monomers as acrylic acid,methacrylic acid, itaconic anhydride and fumaric acid polymerize toofast for the successful practice of this invention. If, however, theolefinic bond is conjugated but otherwise deactivated as by alkylsubstitution, the monomer can be used in this application. Anon-limiting example of such a conjugated but deactivated monomer iscyclohex-1-ene, 2-dicarboxylic anhydride.

The copolymers consist of about 70-99.95 weight percent of polyolefinand about 0.05-30 weight percent of the cyclic unsaturated acid or acidanhydride or mixtures and these resulting graft copolymers are capableof blending or reacting with a wide variety of other materials to modifythe copolymer further.

The polyolefin used in making the graft polymer carrier material used inthis invention may comprise a polyethylene homopolymer with a density ofat least about 0.940-0.965 and may be essentially linear.

The polyolefin may also comprise a terpolymer such as one of ethylene,propylene and up to about 5 weight percent of a cyclic or acyclicaliphatic diene or mixtures thereof.

Excellent monomers in the graft copolymer of this invention include4-methylcyclohex-4-ene-1,2-dicarboxylic acid anhydride,tetrahydrophthalic anhydride, x-methylnorborn-5-ene-2,3-dicarboxylicanhydride, norborn-5-ene-2,3-dicarboxylic anhydride, 2-cyclopentenylacetic acid, abietic acid, maleopimaric acid andbicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride.

Methods of preparing graft copolymers such as described above are setforth in detail in Wu et al. U.S. Pat. No. 3,873,643.

CATALYST FORMING REACTANTS

The catalyst of the invention comprises the reaction product of (1) analkyl aluminum halide, (2) a dialkyl magnesium compound or complex, and(3) a titanium alkoxide, alkoxide halide or halide, supported on anorganic carrier as described above and used in the presence of anorganometallic co-catalyst, preferably an alkyl aluminum compound. Thereaction of the three components may be carried out at room temperatureor below in the presence of carrier particles and is conducted in asuitable solvent such as isobutane, for example.

The alkyl aluminum halide is chosen from the group comprising dialkylaluminum halides, alkyl aluminum sesquihalides and alkyl aluminumdihalides. A preferred alkyl aluminum halide is ethyl aluminumsesquichloride.

The dialkyl magnesium compound, which may be in the form of an alkylaluminum complex, is preferably dibutyl magnesium, di-n-hexyl magnesiumor butyl ethyl magnesium.

The titanium compound is an alkoxide, mixed alkoxide halide, or halideof the formula Ti(OR)_(n) X_(4-n) where R is an alkyl group of 1-6carbon atoms, X is a halogen atom, and n is an integer between 0 and 4,inclusive. Titanium tetraisopropoxide is preferred.

Prior catalysts utilizing aluminum chloride or another chloride tend tobe corrosive and require special handling equipment. A washing step isalso required to remove residual chloride from the catalyst. In thepractice of the present invention, the alkyl aluminum halide and thetitanium alkoxide halide, if any, complex with the dialkyl magnesiumcompound to substantially the fullest possible extent regardless of therespective mole ratios of these components over a wide range of ratios,thereby eliminating residue from the catalyst surface, as well aseffecting a reduction in lost titanium and magnesium. Hence no specialequipment is necessary for handling the catalyst of the invention, noris a washing step necessary.

The three reactive components may be in hydrocarbon solution and, whenreacted in the presence of a solvent and polymeric carrier particles ofthe type described, deposit an insoluble reaction product on the surfaceof the particles. The mixing of the reactive materials is preferablydone at or below room temperature. After the mixing is complete, thesolvent is evaporated, preferably by heating above room temperature butat a temperature less than the softening temperature of the polymericcarrier. The evaporation step promotes the formation of particles, asopposed to irregularly sized chunks, in a slurry polymerization reactionutilizing the resulting catalyst, and decreases reactor fouling.

It is normally best to heat the catalyst under inert gas at atemperature of about 90°-100° C. for from 1/2 to 10 hours, or until freeof solvent.

The amount of the titanium component is chosen to give preferably about0.1 to 10% by weight titanium in the reaction product. The respectivequantities of the titanium, magnesium and aluminum halide compounds arepreferably selected such that the weight of the reaction productsupported on the polymeric carrier particles is less than about 30% ofthe total weight of the particles and reaction product. The respectivemole ratios of the alkyl aluminum halide, the dialkyl magnesium and thetitanium compound may be adjusted to give optimum reactivity or tomodify polymer properties.

Further, the mole ratio of the co-catalyst to the solid catalyst may beadjusted, and hydrogen may be supplied to the polymerization reactionsystem to control product molecular weight, as is well-known in the art.

REACTION CONDITIONS

The particle form reaction system is characterized by the introductionof monomer to an agitated catalyst-solvent slurry. The solvent istypically isobutane and the reaction is best carried out in a closedvessel to facilitate pressure and temperature regulation. Pressure maybe regulated by the addition of nitrogen and/or hydrogen to the vessel.Addition of the latter is useful for regulation of the molecular weightof product polymer, as described in the following examples.

Particle form polymerization of ethylene with the catalyst of thisinvention is best carried out at about 105° C. to 110° C. at a pressureof between 35 and 40 atmospheres. In gas phase polymerization, thetemperature may range from less than about 85° C. to about 100° C. witha pressure as low as about 20 atmospheres. Copolymers may be produced byeither process by addition of propylene, butene-1, hexene-1 and similaralpha-olefins to the reactor. Production of copolymers of relatively lowdensity is preferably carried out at a relatively low temperature.

EXAMPLE 1

Pellets of high density polyethylene with 1.33 weight percentX-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride graftedto it, as described in U.S. Pat. No. 3,873,643 and herein identified asXMNA graft, were ground to particles of about 1 mm in diameter. 10 gramsof XMNA particles was charged to a flask from which air was removed byN₂ purge. 20 ml each of cyclohexane and a heptane solution of ethylaluminum sesquichloride (7.7 mmoles Et₃ Al₂ Cl₃) were added whilestirring vigorously.

10 ml of a heptane solution of a dibutyl magnesium/triethyl aluminumcomplex (9.1 mmole magnesium and 1.5 mmole triethyl aluminum) werequickly introduced to a flask while stirring. 2.0 ml (6.64 mmoles) ofpure titanium tetraisopropoxide was added to the resulting slurry, andthe color of the mixture became very dark. The solvent was evaporatedand the catalyst was heat-aged by heating at 90° C. for 30 minutes underthe N₂ purge. The remaining solid material was then tested as asupported ethylene polymerization catalyst.

In a first polymerization test, 0.2230 g of the solid material wascharged, under N₂, to a closed polymerization vessel. 500 ml isobutanewas forced into the vessel and ethylene was added to maintain the totalpressure at 550 psig. The vessel was maintained at 105° C. throughoutthe reaction. In 25 minutes, 6 grams of polyethylene was produced for anhourly reactivity with respect to the solid catalyst of 65 g/g.

In a second polymerization test, the procedure was identical except that0.0958 g of the catalyst and 0.3 ml (0.28 mmole) of triisobutyl aluminum(TIBAL) solution were charged to the polymerization vessel. In thiscase, the reactivity was 910 g/g/hr with respect to the solid catalyst,580 g/g/hr with respect to the total catalyst weight including thetriisobutyl aluminum, and 134,000 g/g/hr with respect to titanium,clearly showing the beneficial effect of using a triisobutyl aluminumco-catalyst. The solid catayst is calculated to be 1.17 weight percenttitanium on a solvent-free basis and the molar ratio of triisobutylaluminum to titanium was 12/1.

EXAMPLE 2

A solid catalyst component was prepared according to the proceduredescribed in Example 1, except that 20 grams of XMNA was used and nocyclohexane was added. An ethylene polymerization test was conducted at105° C. and 550 psig using 0.0838 g of solid catalyst and a 6/1 molarratio of TIBAL to titanium. The hourly catalyst reactivity was 920 g/gand the hourly reactivity based on titanium was 105,000 g/g. The productpolyethylene was predominantly in the form of particles 1 to 2centimeters in diameter, together with a minor amount of fragmentsproduced by the reactor agitator. The bulk density of the product was adesirably high 0.30 g/cm³ and no product particles adhered to thereactor wall.

EXAMPLE 3

A quantity of XMNA graft was ground to approximately 30 mesh in aWiley-type laboratory mill. 10 grams of the resulting powder was thenincorporated in a solid catalyst by the procedure of Example 1. 0.1656 gof solid catalyst was used in an ethylene polymerization test with 1.0ml (0.92 mmole) TIBAL solution. The Al/Ti mole ratio was 22.8/1. Thepolymerization reaction was conducted at 105° C. and 550 psig.

In this test, the total hourly catalyst reactivity was 400 g/g and thetitanium reactivity was 77,200 g/g/hr. The product polyethylene was inthe form of particles 3-5 mm in diameter, and none adhered to thereactor walls. With reference to Example 2, it is apparent thatreduction in carrier size effects a reduction in product particle size.The product bulk density was again 0.3 g/cm³.

EXAMPLE 4

The carrier used in this example was XMNA graft ground by a cryogenictechnique and sieved. Only particles which passed through a 140 meshsieve were retained for use in the catalyst. 10 grams of XMNA particleswas added to a nitrogen purged flask, as in Example 1. 10 ml of ethylaluminum sesquichloride solution and 5 ml of the dibutylmagnesium/triethyl aluminum complex solution of Example 1 were rapidlyintroduced while stirring, followed by introduction of 1.0 ml titaniumtetraisopropoxide for a titanium content of 1.17 weight percent on asolvent-free basis. The solvent was evaporated as in Example 1.

0.0905 g solid catalyst was used in an ethylene polymerization testunder conditions identical to those of Example 1 except that the moleratio of TIBAL to titanium was 26/1. The total catalyst reactivity wasfound to be 860 g/g/hr with a titanium reactivity of 179,000 g/g/hr.

EXAMPLE 5

A further polymerization test was made with the catalyst and reactantsof Example 4, with the weight of solid catalyst being 0.0352 g and witha mole ratio of TIBAL to titanium of 25/1. The test was conducted at105° C. and 550 psig. The total catalyst reactivity was 1160 g/g/hr andthe titanium reactivity was 260,000 g/g/hr. The average particle size ofthe product was less than about 1 mm, with the bulk density again being0.3 g/cm³, providing a further illustration of the effect of carrierparticle size on product particle size. (See Examples 2 and 3.)

EXAMPLES 6-9

A supported catalyst was prepared from cryogenically ground XMNA graftas described in Example 4. A series of four polymerization tests wasconducted with this catalyst using a TIBAL to titanium mole ratio ofabout 25/1 and a polymerization temperature of 107° C. After theaddition of solid catalyst and TIBAL, isobutane was introduced into theclosed reaction vessel, followed by ethylene. In three runs, hydrogenwas added to the reactor to increase the pressure by the amount statedbelow followed by more ethylene to maintain the pressure at 550 psig.The resulting reactivities are given below:

    ______________________________________                                                   Catalyst Hourly Reactivity                                                    (g/g/hr)                                                           Exam. Hydrogen   Total                                                        No.   Added      Catalyst  Titanium                                                                              HLMI   MI                                  ______________________________________                                        6     0          1620      280,500 0.1    --                                  7     100 psig   440        76,500 --     6.9                                 8      75 psig   710       123,300 --     4.0                                 9      50 psig   660       115,600 --     1.6                                 ______________________________________                                    

The number of vinyl groups in the product of Example 7 was found to be0.40/2000 carbon atoms. This example illustrates that the melt index ofproduct polyethylene is directly related to hydrogen partial pressure inthe reaction system. Moreover, vinyl unsaturation of the product isshown to be desirably low, thereby increasing the resistance of theproduct polymer to oxidative degradation under processing conditions.

EXAMPLES 10-11

The solid catalyst used in these examples was the same as used inExamples 6-9. The co-catalyst was a mixture of TIBAL and diethylzinc(DEZ). In each run, 50 psig partial pressure of hydrogen was added tothe reactor and the temperature and total pressure were maintained at109° C. and 550 psig, respectively. The results are given below:

    ______________________________________                                                               Catalyst Hourly Reactivity                             Exam.                  (g/g/hr)                                               No.    Co-catalyst     Catalyst  Titanium                                                                             MI                                    ______________________________________                                        10       0.43 mmole TIBAL                                                                            820       161,200                                                                              1.3                                          + 0.17 mmole DEZ                                                       11       0.18 mmole TIBAL                                                                            310        73,500                                                                              1.8                                          + 0.18 mmole DEZ                                                       ______________________________________                                    

In Example 10, the weight of solid catalyst was 0.0786 g and 0.0498 g ofcatalyst was used in Example 11. The titanium weight percentage was1.17% in each case. These examples show that a mixture of alkyl zinc andaluminum compounds may be used as a co-catalyst without significantlyaffecting the melt index of the product polyethylene.

EXAMPLE 12

The carrier of this example was a polyolefin powder with an impactmodifier generally used in rotational molding applications. The carrierhad a density of about 0.950 g/cm³ and a melt index of 6.5. Ten grams ofcarrier was mixed with ethyl aluminum sesquichloride, dibutylmagnesium/triethyl aluminum complex solution and titaniumtetraisopropoxide, as described in Example 4. After evaporation ofsolvent as described in Example 1, 0.0718 g of the resulting solidcatalyst and 0.42 ml of TIBAL solution (0.92 M in heptane) wereintroduced to a polymerization vessel and an ethylene polymerization wasconducted at 105° C. and a total pressure of 550 psig with 50 psighydrogen partial pressure.

The reaction was continued for 90 minutes to yield 160 grams ofpolyethylene particles having a bulk density of 0.33 g/cm³. The hourlyreactivity was 185,600 g/g based on titanium and 1700 g/g based on totalcatalyst. The melt index was 4.8 and the high load melt index was 101. Arelatively low ratio of high load to normal melt index of 21 indicates arelatively narrow molecular weight distribution and a desirably lowproduct shear sensitivity.

EXAMPLE 13

A polymerization test was conducted with the solid catalyst of Example12. A heptane solution of trihexylaluminum was substituted for TIBAL asthe co-catalyst. The molar ratio of trihexylaluminum to titanium was15.7/1. 50 psig of hydrogen was added, followed by the introduction ofethylene, and the reaction was conducted at 105° C. and 550 psig totalpressure. The hourly reactivity based on solid catalyst was 1200 g/g and99,300 g/g based on titanium. The melt index was 2.4, the high load meltindex was 79, and the ratio of high load melt index to melt index was32.8. The product bulk density was 0.26 g/cm³.

EXAMPLE 14

An ethylene polymerization test was conducted with the solid catalyst ofExample 12. The co-catalyst was diisobutyl aluminum hydride in molarratio to titanium of 15.7/1. The polymerization conditions wereidentical to those of Example 9. The hourly reactivity based on solidcatalyst was 1010 g/g and 84,500 g/g based on titanium. The melt indexwas 3.7 and the high load melt index was 95.1, for a ratio of high tonormal melt index of 26. The product bulk density was 0.31 g/cm³.

EXAMPLE 15

In this example, the carrier was a sample of the cryogenically groundXMNA graft of Examples 6-9. 10 grams of the XMNA graft was charged to anN₂ purged flask and air was removed, followed by addition of 1.0 ml oftitanium tetraisopropoxide. The mixture was then heated with a hot airgun under N₂ purge until condensation of liquid on the upper portion ofthe flask ceased. 10 ml of a heptane solution of ethyl aluminumsesquichloride (15.4 mmoles Al) and 10 ml of a heptane solution ofdibutyl magnesium/aluminum complex (4.6 mmoles Bu₂ Mg and 0.75 mmolesAl) were added. Solvent was evaporated by bath heating of the catalystat 100° C. for 30 minutes under an N₂ purge to result in a solvent-freesolid catalyst.

In an ethylene polymerization test, 0.0457 g of solid catalyst was mixedwith 0.27 ml (0.25 mmole) of TIBAL solution and 50 psig hydrogen wasadded as previously described. The reaction was run for 150 minutes at105° C. and a total pressure of 550 psig. The hourly yield was 1050 g/gbased on solid catalyst and 88,000 g/g based on titanium.

A sample of the polymer was pyrolized under standard conditions to leavean ash of 60 ppm. This ash level is satisfactory for all commercialapplications, and thus it is demonstrated that the removal of catalystresidues is unnecessary. It has been found, however, that if thesupported reaction product catalyst exceeds about 30 weight percent ofthe total of the reaction product and the polymeric carrier, anunsatisfactory ash level results.

The melt index of the product was 2.7, the high load melt index was 77,and the radio of the two was 28.4/1. The bulk density was 0.31 g/cm³ andthe number of vinyl groups was 0.4 per 2000 carbon atoms. This exampleillustrates that the order of mixing of the three reagents with thecarrier does not affect catalytic activity. Other mixing sequences werealso tested with similar results.

EXAMPLE 16

In this example a finely divided high density polyethylene with anaverage particle size of about 20 microns was used as the carrier. A 10gram quantity of the powder was introduced to a flask purged of air bystirring under an N₂ stream for 30 minutes at room temperature. Threecatalyst forming reactants were added to the flask in the followingorder, while agitation by a magnet bar continued:

(1) 10 ml of 25% ethyl aluminum sesquichloride in heptane;

(2) 10 ml of 10% dibutyl magnesium-triethyl aluminum complex in heptane;and

(3) a volume of pentane solution containing 0.1 ml of titaniumtetraisopropoxide

The solvent was evaporated by heating for 30 minutes at 90° C. under aflow of dry N₂. The calculated titanium concentration of this materialwas 0.10 weight percent.

3.0 ml of a 25% TIBAL solution per gram of solid catalyst was added anda particle form ethylene polymerization test was conducted at 105° C.and a total pressure of 550 psig with 50 psig hydrogen. The totalcatalyst reactivity including the TIBAL was 1244 g/g/hr and thereactivity based on titanium was 1,525,000 g/g/hr. The melt index of theparticle form product was 0.20.

EXAMPLE 17

A catalyst was prepared by using the XMNA graft carrier of Example 4. 10grams of the powder was purged with N₂ and subsequently combined with7.5 ml of ethyl aluminum sesquichloride solution (5.8 mmoles inheptane), 6.5 ml of butyl ethyl magnesium (3.85 mmoles in heptane) and0.6 ml of pentane solution containing 0.33 mole of titaniumtetraisopropoxide. The solvent was evaporated by heating under N₂ for 30minutes at a temperature of 90° C. The calculated titanium content ofthis material was 0.11 weight percent.

An ethylene polymerization test was conducted as previously described at105° C. and 550 psig total pressure, with 75 psig hydrogen. The totalcatalyst reactivity was 1000 g/g/hr and the reactivity with respect totitanium was 1,170,000 g/g/hr. The melt index of the productpolyethylene was 1.14.

EXAMPLE 18

10 g of Microthene high density polyethylene powder was added to a dry,nitrogen purged flask and agitated with a magnet bar for one hour whilemaintaining the nitrogen purge. The following reactants were addedsuccessively at room temperature while agitating continued:

(1) 7.5 ml of 25% ethyl aluminum sesquichloride in heptane;

(2) 6.5 ml of 10% of butyl ethyl magnesium in heptane; and

(3) 0.10 ml of titanium tetrachloride.

The composition was stirred for a few minutes to give a uniform color,followed by evaporation of the heptane solvent by immersion of the flaskin an ethylene glycol bath for 30 minutes at 90° C. under the nitrogenflow.

A quantity of the resulting catalyst was tested in a batch reactor underparticle form conditions. The polymerization temperature was 221° F.,and total pressure was maintained at 550 psig with a hydrogen partialpressure of 50 psig. 9.2 mmoles of TIBAL co-catalyst per gram of solidcatalyst component was used. The yield of particle form polyethylenebased on the solid component was 421 g/g/hr and the reactivity based ontitanium was 119,000 g/g/hr.

EXAMPLE 19

A reaction mixture of titanium tetrachloride and titaniumtetraisopropoxide in amounts selected to result in an averagecomposition corresponding to titanium diisopropoxide dichloride wasprepared, as follows. One milliliter (3.32 mmoles) of titaniumtetraisopropoxide was added to 18 ml of dry heptane under a nitrogenatmosphere. 0.38 milliliter (3.38 mmoles) of titanium tetrachloride wasthen added and a white precipitate formed. The reaction mixture wasmaintained at room temperature for one hour.

10 g quantity of cryogenically ground XMNA powder was put into a dry,nitrogen purged flask. The powder was stirred for one hour under thenitrogen purge, and the following were added during stirring in thefollowing order:

(1) 7.5 ml of 25% ethylaluminum sesquichloride in heptane;

(2) 10.0 ml of an 8.9% solution of a magnesium/aluminum complex of theformula (Bu₂ Mg)₆.1 (Et₃ Al) in heptane; and

(3) 2.0 ml of the above described titanium diisopropoxide dichloridereaction mixture.

As soon as the third reactant was added, the flask was immersed in aheating bath at 90° C. for 30 minutes and heptane was evaporated undernitrogen purge.

A quantity of the resulting catalyst was tested in a batch reactor underparticle form polymerization conditions at 215° F. and a total pressurewas 550 psig with 50 psig hydrogen partial pressure. 2.7 mmoles of TIBALco-catalyst per gram of solid XMNA catalyst was used.

The polyethylene yield based on solid catalyst was 687 g/g/hr, and thereactivity based on titanium was about 254,000 g/g/hr. The productpolyethylene was granular and of a substantially uniform particle size.

All parts and percentages herein are by weight.

Abbreviations used herein to identify chemical ingredients and productcharacteristics include:

DEZ--diethylzinc

HLMI--high load melt index

MI--melt index

TIBAL--Triisobutylaluminum

XMNA--an X-methyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acidanhydride grafted polyethylene, as described in U.S. Pat. No. 3,873,643.

I claim:
 1. A supported olefin polymerization and copolymerizationcatalyst active in the presence of an organometallic co-catalystprepared by mixing reactive materials comprising a lower alkyl aluminumhalide, a dialkyl magnesium compound and a reducible titanium compoundof the formula Ti(OR)_(n) X_(4-n) where R is an alkyl group, X is ahalogen atom, and n is an integer between 0 and 4, inclusive, in thepresence of a solvent and a particulate organic polymer to form areaction product supported on said particles, said particulate organicpolymer comprising a graft copolymer of about 70-99.95 weight percent ofa polyolefin polymer and about 30-0.05 weight percent of at least onemonomer selected from the group consisting of polymerizable cyclic andpolycyclic ethylenically unsaturated carboxylic acids and carboxylicacid anhydrides, and evaporating said solvent at a temperature which isless than the softening temperature of said organic polymer.
 2. Thecatalyst of claim 1 wherein less than about 5% by weight of the total ofsaid reaction product and said organic polymer particles comprisestitanium.
 3. The catalyst of claim 1 wherein about 0.1-10% by weight ofthe total of said reaction product and said organic polymer particlescomprises titanium.
 4. The catalyst of claim 1 wherein said lower alkylaluminum halide is chosen from the group consisting essentially ofdi-lower alkyl aluminum halides, lower alkyl aluminum sesquihalides andlower alkyl aluminum dihalides.
 5. The catalyst of claim 4 wherein saidlower alkyl aluminum halide comprises ethyl aluminum sesquichloride. 6.The catalyst of claim 1 wherein said dialkyl magnesium compoundcomprises dibutyl magnesium.
 7. The catalyst of claim 1 wherein saiddialkyl magnesium compound comprises di-n-hexyl magnesium.
 8. Thecatalyst of claim 1 wherein said dialkyl magnesium compound comprisesbutyl ethyl magnesium.
 9. The catalyst of claim 1 wherein said dialkylmagnesium compound comprises a magnesium complex of trialkyl aluminum.10. The catalyst of claim 1 wherein said titanium compound comprisestitanium tetraisopropoxide.
 11. The catalyst of claim 1 wherein saidtitanium compound comprises titanium tetrachloride.
 12. The catalyst ofclaim 1 wherein said titanium compound comprises a titanium dialkoxydihalide.
 13. The catalyst of claim 12 wherein said titanium dialkoxydihalide comprises titanium diisopropoxide dichloride.
 14. The catalystof claim 1 wherein said reactive materials are present in amounts toproduce a quantity of said reaction product which is less than about 30percent of the total weight of said reaction product and said organicpolymer particles.
 15. A supported olefin polymerization andcopolymerization catalyst active in the presence of an organometalliccocatalyst prepared by mixing reactive materials comprising a loweralkyl aluminum halide, a dialkyl magnesium compound and a reducibletitanium compound of the formula Ti(OR)_(n) X_(4-n) where R is an alkylgroup, X is a halogen atom, and n is an integer between 0 and 4,inclusive, in the presence of a solvent and a particulate organicpolymer consisting essentially of high density polyethylene which haschemically bonded to it between about 0.05 and about 30 weight percentof an organic carboxylic acid or acid anhydride to form a reactionproduct supported on said particles, and evaporating said solvent at atemperature which is less than the softening temperature of said organicpolymer.
 16. The catalyst of claim 15 wherein said organic polymer is anX-methyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydridegrafted polyethylene.
 17. A supported olefin polymerization andcopolymerization catalyst active in the presence of an organometallicco-catalyst prepared by mixing reactive materials comprising a loweralkyl aluminum halide, a dialkyl magnesium compound and a reducibletitanium compound of the formula Ti(OR)_(n) X_(4-n) where R is an alkylgroup, X is a halogen atom, and n is an integer between 0 and 4,inclusive, in the presence of a solvent and a particulate organicpolymer to form a reaction product supported on said particles, saidparticulate organic polymer comprising a graft copolymer of about70-99.95 weight percent of a polyolefin polymer and about 30-0.05 weightpercent of at least one monomer selected from the group consisting ofpolymerizable cyclic ethylenically unsaturated carboxylic acids andcarboxylic acid anhydrides, said reactive materials being present inamounts to produce a quantity of said reaction product which is lessthan about 30 percent of the total weight of said reaction product andsaid organic polymer particles, and evaporating said solvent at atemperature which is less than the softening temperature of said organicpolymer.
 18. The method of preparing a supported olefin polymerizationand copolymerization catalyst active in the presence of anorganometallic co-catalyst comprising mixing reactive materialscomprising a lower alkyl aluinum halide, a dialkyl magnesium compoundand a reducible titanium compound of the formula Ti(OR)_(n) X_(4-n)where R is an alkyl group, X is a halogen atom, and n is an integerbetween 0 and 4, inclusive, in the presence of a solvent and aparticulate organic polymer to form a reaction product supported on saidparticles, said particulate organic polymer comprising a graft copolymerof about 70-99.95 weight percent of a polyolefin polymer and about30-0.05 weight percent of at least one monomer selected from the groupconsisting of polymerizable cyclic and polycyclic ethylenicallyunsaturated carboxylic acids and carboxylic acid anhydrides, andevaporating said solvent at a temperature which is less than thesoftening temperature of said organic polymer.
 19. The catalystpreparation method of claim 18 wherein less than about 5% by weight ofthe total of said reaction product and said organic polymer particlescomprises titanium.
 20. The catalyst preparation method of claim 18wherein about 0.1-10% by weight of the total of said reaction productand said organic polymer particles comprises titanium.
 21. The catalystpreparation method of claim 18 wherein said lower alkyl aluminum halideis chosen from the group consisting essentially of di-lower alkylaluminum halides, lower alkyl aluminum sesquihalides and lower alkylaluminum dihalides.
 22. The catalyst preparation method of claim 21wherein said lower alkyl aluminum halide comprises ethyl aluminumsesquichloride.
 23. The catalyst preparation method of claim 18 whereinsaid dialkyl magnesium compound comprises dibutyl magnesium.
 24. Thecatalyst preparation method of claim 18 wherein said dialkyl magnesiumcompound comprises di-n-hexyl magnesium.
 25. The catalyst preparationmethod of claim 18 wherein said dialkyl magnesium compound comprisesbutyl ethyl magnesium.
 26. The catalyst preparation method of claim 18wherein said dialkyl magnesium compound comprises a magnesium complex oftrialkyl aluminum.
 27. The catalyst preparation method of claim 18wherein said titanium compound comprises titanium tetraisopropoxide. 28.The catalyst preparation method of claim 18 wherein said titaniumcompound comprises titanium tetrachloride.
 29. The catalyst preparationmethod of claim 18 wherein said titanium compound comprises a titaniumdialkoxy dihalide.
 30. The catalyst preparation method of claim 29wherein said titanium dialkoxy dihalide comprises titaniumdiisopropoxide dichloride.
 31. The method of claim 18 wherein thequantities of said reactive materials and said organic polymer areregulated such that said reaction product is less than about 30 percentof the total weight of said reaction product and said organic polymerparticles.
 32. The method of preparing a supported olefin polymerizationand copolymerization catalyst active in the presence of anorganometallic co-catalyst comprising mixing reactive materialscomprising a lower alkyl aluminum halide, a dialkyl magnesium compoundand a reducible titanium compound of the formula Ti(OR)_(n) X_(4-n)where R is an alkyl group, X is a halogen atom, and n is an integerbetween 0 and 4, inclusive, in the presence of a solvent and aparticulate organic polymer consisting essentially of a high densitypolyethylene which has chemically bonded to it between about 0.05 andabout 30 weight percent of an organic carboxylic acid or acid anhydrideto form a reaction product supported on said particles, and evaporatingsaid solvent at a temperature which is less than the softeningtemperature of said organic polymer.
 33. The catalyst preparation methodof claim 32 wherein said organic polymer is an X-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid anhydride graftedpolyethylene.
 34. The method of preparing a supported olefinpolymerization and copolymerization catalyst active in the presence ofan organometallic co-catalyst comprising mixing reactive materialscomprising a lower alkyl aluminum halide, a dialkyl magnesium compoundand a reducible titanium compound of the formula Ti(OR)_(n) X_(4-n)where R is an alkyl group, X is a halogen atom, and n is an integerbetween 0 and 4, inclusive, in the presence of a solvent and aparticulate organic polymer to form a reaction product supported on saidparticles, said particulate organic polymer comprising a graft copolymerof about 70-99.95 weight percent of a polyolefin polymer and about30-0.05 weight percent of at least one monomer selected from the groupconsisting of polymerizable cyclic and polycyclic ethylenicallyunsaturated carboxylic acids and carboxylic acid anhydrides, regulatingthe quantities of said reactive materials and said organic polymer suchthat said reaction product is less than about 30 percent of the totalweight of said reaction product and said organic polymer particles, andevaporating said solvent at a temperature which is less than thesoftening temperature of said organic polymer.